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| United States Patent |
5,300,338
|
|
Byrd, Jr.
, et al.
|
April 5, 1994
|
Coextruded laminates containing polyketone polymers
Abstract
A coextruded laminate may be formed by coextruding a linear alternating
polymer of carbon monoxide and at least one ethylenically unsaturated
hydrocarbon (a polyketone polymer) with an other thermoplastic polymer,
without the use of an adhesive or tie layer, wherein the other
thermoplastic polymer is polyvinylidene fluoride, nylon-6,6, or phenoxy
resin.
| Inventors:
|
Byrd, Jr.; Paul S. (Houston, TX);
Waters; Dixie G. (Houston, TX)
|
| Assignee:
|
Shell Oil Company (Houston, TX)
|
| Appl. No.:
|
880948 |
| Filed:
|
May 8, 1992 |
| Current U.S. Class: |
428/36.6; 428/423.1; 428/474.9; 428/476.3; 428/501; 428/542.8 |
| Intern'l Class: |
B29D 022/00 |
| Field of Search: |
428/421,474.9,349,423.1,461,36.6,501,542.8,476.3
525/529,55,179,426
528/392
|
References Cited
U.S. Patent Documents
| 4585701 | Apr., 1986 | Bartoszek et al. | 428/421.
|
| 4600614 | Jul., 1986 | Lancaster et al. | 428/349.
|
| 4647509 | Mar., 1987 | Wallace et al. | 428/474.
|
| 4678713 | Jul., 1987 | Lancaster et al. | 428/421.
|
| 4808678 | Feb., 1989 | Lutz | 525/529.
|
| 4816514 | Mar., 1989 | Lutz | 525/55.
|
| 4818786 | Apr., 1989 | Gergen et al. | 525/55.
|
| 4818798 | Apr., 1989 | Gergen | 525/55.
|
| 4839437 | Jun., 1989 | Gergen et al. | 525/426.
|
| 4871618 | Oct., 1989 | Kinneberg et al. | 428/461.
|
| 4880904 | Nov., 1989 | Kinneberg et al. | 528/392.
|
| 4935304 | Jun., 1990 | Danforth | 428/423.
|
| 4996086 | Feb., 1991 | Gerlowski et al. | 428/36.
|
| 5043389 | Aug., 1991 | Gergen et al. | 525/179.
|
| 5064724 | Nov., 1991 | Ofstein | 428/501.
|
| Foreign Patent Documents |
| 191690 | Jan., 1986 | EP.
| |
Primary Examiner: Thibodeau; Paul J.
Assistant Examiner: Le; H. Thi
Attorney, Agent or Firm: Okorafor; James O.
Claims
What is claimed is:
1. A coextruded multi-ply laminate consisting essentially of:
a first polymer layer comprising a linear alternating polyketone polymer of
carbon monoxide and at least one .alpha.-olefin, and
a second polymer layer of polyhexamethyleneadipamide wherein the second
polymer layer is superimposed on and exhibits an interactive adhesion to
the first polymer layer such that the adhesion is too great to allow
separation without destroying one or both layers of polymer.
2. The laminate of claim 1 wherein the polyketone polymer has recurring
units represented by the formula
##STR3##
wherein G is derived from a monomer of an .alpha.-olefin of at least 3
carbon atoms polymerized through the ethylenic unsaturation and the ratio
of y:x is no more than about 0.5.
3. The laminate of claim 2 wherein, in the linear alternating polymer, G is
derived from a monomer of propylene and the ratio of y:x is from about
0.01 to about 0.1.
4. The laminate of claim 2 wherein, in the linear alternating polymer, y is
zero.
5. The laminate of claim 1 wherein the laminate is coextruded in a
cylindrical shape.
6. The laminate of claim 1 wherein the laminate is coextruded into a
parison and blow molded into a container.
7. An article made from the laminate of claim 1.
8. A coextruded laminate of three polymer layers consisting essentially of
a first polymer layer consisting essentially of a linear alternating
polyketone polymer of carbon monoxide and at least one .alpha.-olefin;
a second polymer layer of phenoxy resin which exhibits an interactive
adhesion to the first polymer such that the adhesion is too great to allow
separation without destroying one or both layers of polymer; and
a third polymer layer which is the same as the first polymer layer, wherein
the second polymer layer is located between the first and third polymer
layers.
9. The laminate of claim 8 wherein the polyketone polymer has recurring
units represented by the formula
##STR4##
wherein G is derived from a monomer of an .alpha.-olefin of at least 3
carbon atoms polymerized through the ethylenic unsaturation and the ratio
of y:x is no more than about 0.5.
10. The laminate of claim 9 wherein, in the linear alternating polymer, G
is derived from a monomer of propylene and the ratio of y:x is from about
0.01 to about 0.1.
11. The laminate of claim 9 wherein, in the linear alternating polymer, y
is zero.
12. The laminate of claim 9 wherein the laminate is coextruded in a
cylindrical shape.
13. The laminate of claim 9 wherein the laminate is coextruded into a
parison and blow molded into a container.
14. An article made from the laminate of claim 9.
15. A composite part comprising two or more polymer sections, prepared by
injection molding a first polymer consisting essentially of a linear
alternating polyketone polymer of carbon monoxide and at least one
.alpha.-olefin; and a second polymer consisting essentially of nylon-6,6
wherein the first and second polymer sections adhere to each other without
the use of an adhesive or tie layer.
16. The composite part of claim 15 wherein the polyketone polymer has
recurring units represented by the formula
##STR5##
wherein G is derived from a monomer of an .alpha.-olefin of at least 3
carbon atoms polymerized through the ethylenic unsaturation and the ratio
of y:x is no more than about 0.5.
17. The composite part of claim 16 wherein, in the linear alternating
polymer, G is derived from a monomer of propylene and the ratio of y:x is
from about 0.01 to about 0.1.
18. The composite part of claim 16 wherein, in the linear alternating
polymer, y is zero.
Description
FIELD OF THE INVENTION
This invention relates to polyketone polymers, and, more particularly, to a
coextruded product of a polyketone polymer and an other thermoplastic
polymer. These coextruded products are prepared without the use of an
adhesive or tie layer, yet still exhibit strong adhesion between the
layers.
BACKGROUND OF THE INVENTION
Coextrusion of multiple layers of different polymers through a common die
is used to produce a variety of polymer products, such as sheet, film,
coatings, profiles, pipe, tubing, and foam-core products. Food and
beverage packaging is a common application of such coextruded products.
Sheet or film, for example, are often shaped after coextrusion into
various packaging items by methods such as thermoforming, solid-phase
pressure forming, or stamping. Preparation of tubing and hoses for use in
automobiles and industrial equipment is another application. Individual
polymers exhibit a wide variety of properties, such as permeability to
oxygen, water vapor, and other gases and liquids, and chemical resistance
to acids, bases, hydrocarbons, oils, alcohols, and other materials.
Coextrusion of multiple polymer layers can be used to prepare a product
with optimum properties for a particular application.
No comprehensive theory exists for predicting inter-layer adhesion in
coextrusion of different polymers. Most knowledge comes from
trial-and-error testing of the polymers. Even materials which form
compatible blends do not necessarily exhibit good adhesion when
coextruded. For example, a polyketone polymer and an ethylene vinyl
alcohol copolymer will form a compatible blend, but will not adhere when
coextruded. Adhesive polymers are commonly used as "tie layers" to bond
incompatible polymers that do not normally adhere to each other.
Ethylene-vinyl acetate, ethylene-acrylic acid, and ethylene-methyl
acrylate copolymers are commonly used as tie layers.
Coextrusion of polymers without the use of tie layers allows the use of
simpler equipment, and production of a lower cost product. It is an object
of this invention to provide a coextruded product of two or more
dissimilar polymer layers, produced without the use of any tie layers.
In an analogous processing technique, injection molding may be used to form
composite parts by injecting two or more polymers into the same mold to
make a composite part. The specialized techniques used to produce such
composite parts include coinjection, dual shot, multi-shot, and shuttle
molding. As an alternative, a pre-molded article may be inserted into a
larger mold cavity, and a second polymer injected into the larger mold,
coating part or all of the surface of the premolded article. This
technique is known as insert molding. In the fabrication of such composite
parts, it is essential to have strong adhesion between the different
polymer surfaces to maintain the integrity of the product molded article.
It is another object of this invention to provide a composite part,
prepared through injection molding of two or more dissimilar polymers and
without the use of any adhesive or tie layer between the dissimilar
polymers.
In particular, it is an object of this invention to provide a coextruded
product or composite part of a polyketone polymer and an other
thermoplastic polymer, produced without the use of any adhesive or tie
layer. Surprisingly, after extensive trial-and-error testing, only a few
other thermoplastic polymers have been found that meet this objective.
SUMMARY OF THE INVENTION
The present invention provides a coextruded laminate of a polyketone
polymer and an other thermoplastic polymer, wherein the two polymers
exhibit strong adhesion without the use of an adhesive or tie layer. The
present invention also includes a composite part of two or more polymer
sections, prepared by injection molding a polyketone polymer and an other
thermoplastic polymer, wherein adjacent sections of the composite part
adhere to each other without the use of any adhesive or tie layer. The
other thermoplastic polymers of the invention include polyvinylidene
fluoride, nylon-6,6, and phenoxy resin.
Since no adhesive or tie layer is required, the coextruded laminates may
include only two layers. In one alternative, the laminate may include
three layers, wherein either the other thermoplastic polymer is sandwiched
between two layers of the polyketone polymer, or the polyketone polymer is
sandwiched between two layers of the other thermoplastic polymer. In
another alternative, the polyketone polymer may be sandwiched between two
different other thermoplastic polymers of the invention. Multi-ply
laminates which include one or more layers of polyketone polymer and one
or more layers of an other thermoplastic polymer, wherein the multi-ply
laminate includes superimposed layers of a polyketone polymer and an other
thermoplastic polymer adhered to each other without the use of an adhesive
or tie layer, are also considered to be within the scope of this
invention. The coextruded laminates of the invention may be flat, such as
sheet or film; shaped, such as pipe or tubing; or further processed, such
as by blow molding into containers, etc.
The present invention also provides a process for making a coextruded
laminate of two or more layers by coextruding a polyketone polymer with
another thermoplastic polymer, without the use of an adhesive or tie layer
between the polymer layers. A process for making a composite part of two
or more sections, prepared by injection molding a polyketone polymer and
an other thermoplastic polymer, wherein the adjacent sections of
polyketone polymer and other thermoplastic polymer adhere to each other
without the use of any adhesive or tie layer, is also considered within
the scope of this invention.
DETAILED DESCRIPTION OF THE INVENTION
The polyketone polymers of the invention are thermoplastic polymers of a
linear alternating structure and contain substantially one molecule of
carbon monoxide for each molecule of unsaturated hydrocarbon. Hereinafter,
these polymers may be simply referred to as polyketones. Ethylenically
unsaturated hydrocarbons suitable for use as precursors of the polyketone
polymers have up to 20 carbon atoms inclusive, preferably up to 10 carbon
atoms, and are aliphatic such as ethylene and other .alpha.-olefins
including propylene, 1-butene, isobutylene, 1-hexene, 1-octene and
1-dodecene, or are arylaliphatic, containing an aryl substituent on an
otherwise aliphatic molecule, particularly an aryl substituent on a carbon
atom of the ethylenic unsaturation. Illustrative of this latter class of
ethylenically unsaturated hydrocarbons are styrene, p-methylstyrene,
p-ethylstyrene and m-isopropylstyrene.
The preferred polyketone polymers are copolymers of carbon monoxide and
ethylene or terpolymers of carbon monoxide, ethylene and a second
ethylenically unsaturated hydrocarbon of at least 3 carbon atoms,
preferably an .alpha.-olefin such as propylene. When the preferred
polyketone terpolymers are employed, there will be within the terpolymer
at least about 2 units derived from a monomer of ethylene for each unit
derived from a monomer of the second hydrocarbon. Preferably, there will
be from about 10 units to about 100 units derived from a monomer of
ethylene for each unit derived from a monomer of the second hydrocarbon.
The polymer chain of the preferred polyketone polymers has recurring units
represented by the formula
##STR1##
wherein G is derived from the monomer of ethylenically unsaturated
hydrocarbon of at least 3 carbon atoms polymerized through the ethylenic
unsaturation and the ratio of y:x is no more than about 0.5. When
copolymers of carbon monoxide and ethylene are employed in the blends of
the invention, there will be no second hydrocarbon present and the
copolymers are represented by the above formula wherein y is zero. When y
is other than zero, i.e., terpolymers are employed, the--CO--(--CH.sub.2
--CH.sub.2 --)--units and the --CO--(--G--)--units are found randomly
throughout the polymer chain, and preferred ratios of y:x are from about
0.01 to about 0.1. The end groups or "caps" of the polymer chain will
depend upon what materials were present during the production of the
polymer and whether or how the polymer was purified. The precise nature of
the end groups does not appear to influence the properties of the polymer
to any considerable extent, so the polymers are fairly represented by the
formula for the polymer chain as depicted above.
Of particular interest are the polyketone polymers of number average
molecular weight from about 1000 to about 200,000, particularly those of
number average molecular weight from about 20,000 to about 90,000, as
determined by gel permeation chromatography. The physical properties of
the polymer will depend in part upon the molecular weight, whether the
polymer is a copolymer or a terpolymer and, in the case of terpolymers,
the nature and proportion of the second hydrocarbon present. Typical
melting points for the polymers are from about 175.degree. C. to about
300.degree. C., more typically from about 210.degree. C. to about
270.degree. C. The polymers have a limiting viscosity number (LVN),
measured in m-cresol at 60.degree. C. in a standard capillary viscosity
measuring device, from about 0.5 dl/g to about 10 dl/g, more frequently
from about 0.8 dl/g to about 4 dl/g.
The polyketone polymers of the invention may include other polymers in
amounts that are insufficient to reduce the adhesion exhibited between the
polyketone polymers and the other thermoplastic polymers of the invention.
U.S. Pat. No. 4,880,903 (Van Broekhoven et al.) discloses a linear
alternating polyketone terpolymer of carbon monoxide, ethylene, and other
olefinically unsaturated hydrocarbons, such as propylene. Processes for
production of the polyketone polymers typically involve the use of a
catalyst composition formed from a compound of a Group VIII metal selected
from palladium, cobalt, or nickel, the anion of a strong
non-hydrohalogenic acid, and a bidentate ligand of phosphorus, arsenic or
antimony. U.S. Pat. No. 4,843,144 (Van Broekhoven et al.) discloses a
process for preparing polymers of carbon monoxide and at least one
ethylenically unsaturated hydrocarbon using a catalyst comprising a
compound of palladium, the anion of a non-hydrohalogenic acid having a pKa
of below about 6 and a bidentate ligand of phosphorus.
The carbon monoxide and hydrocarbon monomer(s) are contacted under
polymerization conditions in the presence of a catalyst composition formed
from a compound of palladium, the anion of a non-hydrohalogenic acid
having a pKa (measured in water at 18.degree. C.) of below about 6,
preferably below 2, and a bidentate ligand of phosphorus. The catalyst
composition may be formed from a variety of materials, but without wishing
to be limited, a preferred palladium compound is a palladium carboxylate,
particularly palladium acetate, a preferred anion is the anion of
trifluoroacetic acid or p-toluenesulfonic acid and a preferred bidentate
ligand of phosphorus is 1,3-bis(diphenylphosphino)propane or
1,3-bis[di(2-methoxyphenyl)phosphino]propane.
The polymerization to produce the polyketone polymer is conducted in an
inert reaction diluent, preferably an alkanolic diluent, and methanol is
preferred. The reactants, catalyst composition and reaction diluent are
contacted by conventional methods such as shaking, stirring or refluxing
in a suitable reaction vessel. Typical polymerization conditions include a
reaction temperature from about 20.degree. C. to about 150.degree. C.,
preferably from about 50.degree. C. to about 135.degree. C. The reaction
pressure is suitably from about 1 atmosphere to about 200 atmospheres but
pressures from about 10 atmospheres to about 100 atmospheres are
preferred. Subsequent to polymerization, the reaction is terminated, for
example, as by cooling the reactor and contents and releasing the
pressure. The polyketone polymer is typically obtained as a product
substantially insoluble in the reaction diluent and the product is
recovered by conventional methods, such as filtration or decantation. The
polyketone polymer is used as recovered or the polymer is purified, for
example, by contact with a solvent or extraction agent which is selective
for catalyst residues.
The other thermoplastic polymers of the invention are those which exhibit a
strong, interactive adhesion when processed with a polyketone polymer.
Interactive adhesion occurs when the adhesion between the polyketone
polymer and the other thermoplastic polymer is so great that the layers
cannot be separated without destroying one or both layers. For example,
when coextruded with a polyketone polymer, such other thermoplastic
polymers will form a laminate that may be flexed, kinked, or cut, and the
layers will continue to act like a single unit. Thermoplastic polymers
which exhibit such a strong, interactive adhesion with a polyketone
polymer include polyvinylidene fluoride, nylon-6,6, and phenoxy resins.
The thermoplastic polyvinylidene fluoride of the invention is produced from
monomer units of vinylidene fluoride. The polyvinylidene fluoride is
preferably a homopolymer of vinylidene fluoride. Alternatively, a
copolymer of at least 90 mole % vinylidene fluoride is suitable where the
remainder is produced from other fluorinated monomer units, such as
tetrafluoroethylene, hexafluoropropylene, or vinyl fluoride.
Polyvinylidene fluoride polymers are well known in the art, and are
produced by conventional methods. Such polymers are also commercially
available, e.g. Kynar.RTM. 460, manufactured by Atochem.
The nylon of the invention is nylon-6,6, a condensation product of adipic
acid and hexamethylenediamine. Nylon-6,6 is a thermoplastic polyamide
polymer, also known as polyhexamethyleneadipamide, or
poly(hexamethylenediamine-coadipic acid), or
poly(iminohexamethyleneiminoadipoyl). Nylon-6,6 is well known in the art,
and is produced by conventional methods. Nylon-6,6 is also commercially
available, e.g. Zytel.RTM. 101, manufactured by DuPont Polymers.
The family of thermoplastic polyamides also includes nylon-4,6, nylon-6,
nylon-11, nylon-12, and nylon-6,12. These other thermoplastic polyamides
may be blended with the nylon of the invention in small amounts that are
insufficient to reduce the adhesion to polyketones exhibited by the neat
nylon-6,6.
The phenoxy resin of the invention is a high molecular weight thermoplastic
polymer derived from a bisphenol and epichlorohydrin. The number average
molecular weights of the phenoxy resins are typically about 45,000, while
those of epoxy thermoset resins are typically no more than 8,000. The
phenoxy resins also lack the terminal epoxide functionality of the epoxy
resins, and are therefore thermally stable. Phenoxy resins may be
classified as polyols or polyhydroxyethers, and have the general formula:
##STR2##
wherein n is typically at least about 100. Phenoxy resins are well known
in the art, and are produced by conventional methods. Such polymers are
also commercially available, e.g. Ucar.RTM. PKHH, manufactured by Union
carbide Chemicals and Plastics.
The polymers of the invention may also include conventional additives such
as antioxidants and stabilizers, dyes, fillers or reinforcing agents, fire
resistant materials, mold release agents, colorants and other materials
designed to improve the processability of the polymers or the properties
of the resulting products. Such additives are added prior to, or
concurrent with the processing of the polyketone and the other
thermoplastic polymers.
Coextrusion techniques and equipment are well known in the art. Coextrusion
involves the extrusion of molten or plastified polymers through adjacent
or multimanifold dies, such that the extrudates, still in molten,
semi-molten, or plastified form, are brought together to form multi-ply
laminates. The feedblock and die(s) must be designed to preserve layer
thicknesses as the molten polymers move downstream. The thickness of each
ply usually is in the range of about 0.05 mils to about 50 mils or more,
depending on the desired end use. The plies can be of the same thickness,
or different. The material used in each ply is usually different from any
adjacent ply, but can be repeated in the same multi-ply laminate. Film
laminates typically have a thickness of from about 0.5 mils to about 10
mils, while sheet laminates (which are frequently used for thermoforming,
typically have a thickness of from about 10 mils to about 100 mils or
more. Similar techniques are used to produce both flat articles, such as
film and sheet, shaped articles for packaging and other uses, and
profiles, such as pipe and tubing.
The subject invention may also be exploited through use of other methods,
such as insert molding, injection molding, and blow molding. For example,
adhesion between the polyketone and other thermoplastic polymers may be
achieved by applying a molten layer of one polymer onto a finished
artifact or solid insert prepared from the other polymer. Two-shot
injection molding may be used to prepare shaped articles that would
contain layers or sections of polyketone and other thermoplastic polymers,
or an article of one polymer encapsulated within the other polymer. A
cross-head die, for example, may be used to extrude one molten polymer
over a rod or tube made from the other polymer. Blow molding, for example,
involves placing a molten coextruded polymer tube or parison in a mold,
and applying sufficient air pressure inside the parison to force it into
the shape of the mold. Blow molding is particularly suitable for making
bottles and other containers, toys, and various industrial items. These
and other methods may be utilized to exploit the adhesion between
polyketone and other thermoplastic polymers.
The method of producing the articles of the invention is not material so
long as the laminates or other articles are produced without undue
degradation of the polymer components.
The invention is further illustrated by the following Examples which should
not be regarded as limiting.
EXAMPLE 1
A linear alternating terpolymer of carbon monoxide, ethylene, and propylene
(DP MX500) was produced in the presence of a catalyst composition formed
from palladium acetate, trifluoroacetic acid, and
1,3-bis[di(2-methoxyphenyl)phosphino]propane. The polyketone polymer had a
melting point of about 220.degree. C. and an LVN of about 1.8 dl/g when
measured in m-cresol at 60.degree. C. The polyketone polymer also
contained conventional additives.
EXAMPLE 2
Bilayered tubing was made from the polyketone polymer of Example 1 and a
polyvinylidene fluoride polymer. For comparison, bilayered tubing was also
made with a polyvinyl chloride polymer (not of the invention). The
polyvinylidene fluoride polymer was manufactured by Atochem North America,
and the polyvinyl chloride was a rigid or unplasticized grade manufactured
by Westlake.
The bilayered tubing was made in a coextrusion process which utilized two
Killion single-screw extruders. The compression ratio of the extruders was
3:1, and the length to diameter ratio was 24:1. A 1.5 inch diameter
extruder was used to process the substrate polymer, and a 1 inch diameter
extruder was used for the coating polymer. Both extruders fed into a
single manifold coextrusion die. Best results with this type of die were
obtained by starting the 1 inch diameter coating extruder first, followed
by the 1.5 inch diameter substrate extruder, to prevent plugging in the
die. The coextruded tubing was pulled at a rate of about 20 feet per
minute from the die, through a weir sizer, and into a cooling tank. The
coextruded coating layer was about 10 mils thick, and the coextruded
substrate layer was about 30 mils thick.
The polymers were processed as close as possible to the manufacturer's
specifications. Each halopolymer was extruded as a coating over a molten
polyketone substrate. The polyketone polymer was processed at a melt
temperature between 232.degree. and 243.degree. C. Different melt and die
temperatures were used for the various coating polymers. The
polyvinylidene fluoride was processed at a melt temperature of about
238.degree. C. and the polyvinyl chloride was processed at a melt
temperature of about 202.degree. C. The die temperature was set at
243.degree. C. for the polyvinyl fluoride/ polyketone coextrusion, and at
232.degree. C. for the polyvinyl chloride/ polyketone coextrusion.
After cooling, the two types of tubing were flexed, kinked, and cut open
longitudinally. The polyvinylidene fluoride and polyketone layers acted as
a single unit and could not be separated. An attempt was made to separate
the polyvinylidene fluoride and polyketone layers, in order to conduct a
"peel" test for adhesion, however adhesion between the two layers was too
great to allow separation without destroying one or both layers of
polymer. This type of adhesion was designated interactive adhesion.
By comparison, the polyvinyl chloride and polyketone layers acted as a
single unit only until the integrity of either layer was impaired. The
tubing could be flexed or kinked without delamination, however, once
either layer was cut, the two layers were easily separated. This type of
adhesion was designated as a mechanical bond (not of the invention).
EXAMPLE 3
Bilayered tubing was made from the polyketone polymer of Example 1 and
nylon-6,6. For comparison, bilayered tubing was also made from nylon-6 and
two blends of nylon-6,6 with nylon-12 (not of the invention). The nylon-6
and nylon-6,6 were manufactured by DuPont Polymers, and the nylon-12 was
manufactured by Huls America. The blends of nylon-6,6 with nylon-12 were
prepared by combining proportionate amounts of the solid polymers prior to
melting and coextruding. The two blends were 10 wt % nylon-6,6 and 90 wt %
nylon-12; and 25 wt % nylon-6,6 and 75 wt % nylon-12. The tubing was made
by the method of Example 2. Each nylon or nylon blend was extruded as a
coating over a molten polyketone substrate. The nylon-6,6 was processed at
a melt temperature of about 288.degree. C., and a die temperature of about
293.degree. C. For the nylon-6 and nylon blends, the melt processing and
die temperatures were: nylon-6, 210.degree. C. and 232.degree. C.; blend
of 25 wt % nylon-6,6 and 75 wt % nylon-12, 213.degree. C. and 241.degree.
C.; blend of 10 wt % nylon-6,6 and 90 wt % nylon-12, 213.degree. C. and
238.degree. C.
Of the nylons evaluated, only the nylon-6,6 exhibited a strong interactive
adhesion with the polyketone polymer. The nylon-6 exhibited a mechanical
bond (as described in Example 2). The two types of tubing made from blends
of nylon-6,6 with nylon-12 were flexed, kinked, and cut open, yet the
layers continued to act as a single unit. However, it was possible to
separate the layers by applying a strong force by hand. This type of
adhesion was designated as a strong resistance to peel (not of the
invention).
EXAMPLE 4
Bilayered tubing was made from the polyketone polymer of Example 1 and a
thermoplastic phenoxy resin manufactured by Union Carbide. For comparison,
bi-layered tubing was also made with a bisphenol A polycarbonate
manufactured by Miles (not of the invention).
The tubing was made by the method of Example 2. Both the phenoxy resin and
polycarbonate polymer were extruded as a coating over a molten polyketone
substrate. The phenoxy resin was processed at a melt temperature of about
204.degree. C. and a die temperature of about 232.degree. C., and the
bisphenol A polycarbonate was processed at a melt temperature of about
260.degree. C. and a die temperature of about 260.degree. C.
The phenoxy resin exhibited a strong, interactive adhesion when processed
with a polyketone polymer. In comparison, the polycarbonate polymer showed
no adhesion when processed with a polyketone polymer. When flexed, the two
layers of the polycarbonate/polyketone tubing acted independently,
resulting in an obvious delamination, or gathering of the surface coating
at the bend.
EXAMPLE 5
The polyketone terpolymer of Example 1 is injection molded on an injection
molding machine to form a small plaque. This small plaque is attached
inside a larger mold. Molten phenoxy resin is slowly injected into the
larger mold containing the polyketone plaque. The other polymer fills the
remaining space within the mold, surrounding the polyketone plaque on all
but one side, and forming a composite plaque. An attempt is made to
separate the phenoxy resin from the polyketone, however, the two materials
cannot be separated.
EXAMPLE 6
For comparison, an attempt was made to prepare bi-layered tubing from a
polyketone polymer and a number of other thermoplastic polymers. However,
none of these materials exhibited any adhesion to the polyketone polymer
of the invention. A list of these polymers (not of the invention) is
included as Table 1. As described in Example 4, a bisphenol A
polycarbonate polymer also showed no adhesion to a polyketone polymer.
It is particularly interesting to note that the ethylene/methyl acrylate
(EMA) copolymer, which is commonly used as a tie layer to joint two
dissimilar polymers, showed no adhesion with a polyketone polymer.
Other embodiments of the invention will be apparent to those skilled in the
art from a consideration of this specification, or by practice of the
invention described herein. It is intended that the specification and
examples be considered as exemplary only, with the true scope and spirit
of the invention being indicated by the following claims.
TABLE 1
__________________________________________________________________________
Polymers Exhibiting No Adhesion to Polyketone Polymers
Polymer Manufacturer Trade Name
__________________________________________________________________________
ethylene/methyl acrylate (EMA)
DuPont Polymers
Vamac .RTM. N-123
copolymer
ethylene/methacrylic acid copolymer
DuPont Polymers
Nucrel .RTM. 535
ethylene/methacrylic acid copolymer,
Dow Chemicals Primacore .RTM. 1460
partially neutralized
ethylene/vinyl alcohol copolymer
Eval Company Eval .RTM. EP F
ethylene/methacrylic acid copolymer,
DuPont Polymers
Surlyn .RTM. 1601
partially neutralized
polyether block esteramide copolymer
Atochem Polymers
Pebax .RTM. 4033
styrene/acrylonitrile copolymer
Monsanto Company
Lustran .RTM. 31
dynamically vulcanized thermoplastic
Advanced Elastomer Systems
Santoprene .RTM. 101/73
polyolefin
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